WO2019221364A1 - Film de polyimide pour substrat de dispositif d'affichage souple possédant d'excellentes caractéristiques de dissipation de chaleur - Google Patents

Film de polyimide pour substrat de dispositif d'affichage souple possédant d'excellentes caractéristiques de dissipation de chaleur Download PDF

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WO2019221364A1
WO2019221364A1 PCT/KR2019/000639 KR2019000639W WO2019221364A1 WO 2019221364 A1 WO2019221364 A1 WO 2019221364A1 KR 2019000639 W KR2019000639 W KR 2019000639W WO 2019221364 A1 WO2019221364 A1 WO 2019221364A1
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polyimide
tfmb
film
ppda
polyimide precursor
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PCT/KR2019/000639
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English (en)
Korean (ko)
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박진영
김경환
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주식회사 엘지화학
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Priority claimed from KR1020180164186A external-priority patent/KR102333188B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020511988A priority Critical patent/JP7167412B2/ja
Priority to US16/649,311 priority patent/US20200274084A1/en
Priority to CN201980004200.5A priority patent/CN111094411A/zh
Priority to EP19803845.7A priority patent/EP3656805A4/fr
Publication of WO2019221364A1 publication Critical patent/WO2019221364A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a polyimide film for a flexible display device substrate having improved heat dissipation characteristics and a method of manufacturing the same.
  • Polyimide (PI) is a polymer with relatively low crystallinity or mostly amorphous structure. It is easy to synthesize, can make thin film, and does not need a crosslinker for curing. It is a polymer material that has excellent heat resistance, chemical resistance, excellent mechanical properties, electrical properties and dimensional stability. It is widely used in electric and electronic materials such as automotive, aerospace, flexible circuit boards, liquid crystal alignment films for LCDs, adhesives and coating agents. have.
  • polyimide is a high-performance polymer material having high thermal stability, mechanical properties, chemical resistance, and electrical properties, and is increasing in interest as a substrate material for flexible dislays.
  • coefficient of thermal expansion should not be negative at a temperature of 350 °C or more in order to lower the failure rate due to the residual stress of the substrate in the heat treatment process. Therefore, many studies have been conducted to minimize optical characteristics and thermal hysteresis while maintaining basic characteristics of polyimide.
  • polyimide of BPDA (3,3 ', 4,4'-Biphenyltetracarboxylic dianhydride) -PDA (phenylene diamine) component which is a polyimide having excellent heat resistance, is mainly used.
  • a flexible display device such as a TFT device, is fabricated by forming a multilayer inorganic film such as a buffer layer, an active layer, and a gate insulator on a cured polyimide substrate.
  • the polyimide substrate used for the flexible display of the OLED type is more vulnerable to afterimages than the glass substrate.
  • the cause of the afterimage is estimated to be the current variation due to the shift of the threshold voltage V th in the current driving OLED display.
  • the present inventors have found that during the study to solve the afterimage problem, the shift of V th is further intensified by the heat generated during the TFT driving.
  • Plastic substrates such as polyimide substrates, have lower thermal diffusivity and thermal conductivity characteristics than glass substrates, and thus cannot easily dissipate heat generated in LTPS TFT driving than glass substrates. Therefore, when the OLED is used for a long time, the electrical stress of the substrate material due to the electromagnetic field caused by the long-term operation of the TFT device increases, and the temperature of the TFT increases. As a result, in the TFT device having an increased temperature, current fluctuation occurs at a gate voltage, resulting in deterioration of image sticking characteristics.
  • the heat dissipation generated in the TFT device can be improved by improving the heat dissipation characteristics of the plastic substrate material, and the change in Vth shift due to the heat generated in the device can be minimized.
  • the present invention is to provide a polyimide film that can alleviate the shift of the Vth by improving the heat dissipation characteristics, that is, the thermal conductivity and thermal diffusivity in order to solve the above problems.
  • the present invention is to provide a method for producing the polyimide film.
  • the present invention is to provide a flexible display device comprising the polyimide film as a substrate.
  • the present invention to solve the above problems,
  • the thermal diffusivity of the film may be 0.07 mm 2 / s or more.
  • the thermal conductivity of the film may be 0.15 W / m ⁇ K or more.
  • the molar ratio of 4,4'-paraphenylenediamine (pPDA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) may be 90:10 to 95: 5.
  • the molar ratio of biphenylcarboxylic dianhydride (s-BPDA) may be between 100: 98.9 and 100: 98.75.
  • the phthalic anhydride is 0.02 to 0.025 molar ratio relative to 1 mole of the total of 4,4'-paraphenylenediamine (pPDA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) It may be reacted.
  • pPDA 4,4'-paraphenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • the present invention also relates to 4,4'-paraphenylenediamine (pPDA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 3,3 ', 4,4,'-ratio in a polymerization solvent.
  • pPDA 4,4'-paraphenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • 3,3 ', 4,4,'-ratio in a polymerization solvent.
  • Preparing a polyimide precursor by adding a phthalic anhydride (PA) as an end-blocking agent and a polymerization component comprising phenylcarboxylic dianhydride (s-BPDA);
  • PA phthalic anhydride
  • s-BPDA polymerization component comprising phenylcarboxylic dianhydride
  • It provides a method for producing a polyimide film comprising the step of drying and heating the applied polyimide precursor solution.
  • the final curing temperature may be 450 °C or more.
  • a flexible display device comprising the polyimide film.
  • the present invention provides a flexible display device having improved heat dissipation characteristics by providing a polyimide prepared by encapsulating terminals with phthalic anhydride (PA) using p-PDA and TFMB as diamine and s-BPDA as acid dianhydride, and having a crystallinity of 0.5 or more.
  • a substrate for use can be provided.
  • the film according to the present invention can minimize the change of the Vth shift due to heat generated in the device by simply preparing a polyimide film having a higher degree of crystallinity than a polyimide film prepared with an excessive amount of diamine.
  • FIG. 1 schematically illustrates the relationship between crystallinity and heat dissipation characteristics of a film.
  • a polyimide film for flexible display device substrates comprising (TFMB) as a polymerization component, made of polyimide end-sealed with phthalic anhydride, and having a crystallinity of 0.5 or more.
  • polyimide having a BPDA-PDA-TFMB copolymer as the main component is in-plane (in It has been found that the polymer chain orientation in the -plain direction can be improved, and the use of endcapper phthalic anhydride can improve the polymer chain ordering out of plain (see FIG. 1). ). This improvement in crystallinity eventually leads to an increase in thermal diffusivity and thermal conductivity of the polyimide used as the substrate material.
  • the present invention provides a main chain of BPDA-pPDA-TFMB to provide a polyimide having improved mechanical properties while improving heat dissipation characteristics. Crystallinity was improved to 0.5 or more by endcapping with phthalic anhydride (PA).
  • PA phthalic anhydride
  • 'crystallinity (Xcr)' is also referred to as 'crystallinity', it can be obtained by the following equation 1 using GI-XRD.
  • I c is the area under the crystalline peak and I a is the area under the amorphous peak.
  • TOPAS version 4.2 program was used to obtain crystalline and amorphous peaks in the XRD graph as shown in FIG.
  • the TOPAS program can be used to capture crystalline peaks (2 ⁇ ⁇ 18.4 °, 21.3 °, 25.5 °, 28.1 °) in the range of 8 ° ⁇ 2 ⁇ ⁇ 35 °, and obtain the respective areas to calculate the crystallinity therefrom.
  • the film according to the invention may have a thermal diffusivity of at least 0.07 mm 2 / s, or at least 0.08 mm 2 / s or at least 0.09 mm 2 / s.
  • Thermal diffusivity can be measured using LFA 467 Hyperflash at room temperature. The higher the thermal diffusivity, the better the heat dissipation.
  • the film according to the present invention may have a thermal conductivity of 0.2 W / mK or more.
  • the thermal conductivity can be obtained by Equation 2 below, and the higher the thermal conductivity, the better the heat dissipation characteristics.
  • Equation 2 C, ⁇ and ⁇ represent the specific heat (J / g ⁇ K), density (g / cm 3 ) and thermal diffusivity (mm 2 / sec) of the polyimide film.
  • the molar ratio of 4,4'-paraphenylenediamine (pPDA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) may be about 95: 5 to 90:10, Preferably about 95: 5, more preferably about 90:10.
  • the molar ratio of acid dianhydride (s-BPDA) may be about 100: 98.9 to 100: 98.75, preferably about 100: 98.9, more preferably about 100: 98.75.
  • the phthalic anhydride is preferably from 0.02 to 0.025 for 1 mole of 4,4'-paraphenylenediamine (pPDA) and 2,2'-bis (trifluoromethyl) benzidine (TFMB) in total. Preferably it may be reacted at 0.022 to 0.025 molar ratio.
  • pPDA 4,4'-paraphenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • the crystallinity and heat dissipation characteristics of the polyimide can be maximized in the above-described molar ratio.
  • the present invention also relates to 4,4'-paraphenylenediamine (pPDA), 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 3,3 ', 4,4,'-ratio in a polymerization solvent.
  • pPDA 4,4'-paraphenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • 3,3 ', 4,4,'-ratio in a polymerization solvent.
  • Preparing a polyimide precursor by adding a polymer component including phenylcarboxylic dianhydride (s-BPDA) and phthalic anhydride (PA) as an end-sealing agent;
  • s-BPDA phenylcarboxylic dianhydride
  • PA phthalic anhydride
  • It provides a method for producing a polyimide film comprising the step of drying and heating the applied polyimide precursor solution.
  • the final curing temperature may be 450 °C or more.
  • a flexible display device comprising the polyimide film.
  • the 3,3 ', 4,4,'-biphenylcarboxylic dianhydride (s-BPDA), 4,4'-paraphenylenediamine (pPDA) and 2,2'- Bis (trifluoromethyl) benzidine (TFMB) can be polymerized in a molar ratio of 0.98: 1 to 0.99: 1, preferably 0.9875: 1 to 0.9890: 1.
  • phthalic anhydride by adding and reacting phthalic anhydride, heat resistance and permeability can be improved together, and the phthalic anhydride can be polymerized by being added in an amount of 0.02 to 0.025 mole ratio, preferably 0.022 to 0.025 mole ratio with respect to 1 mole of pPDA. have.
  • the method of sealing the terminal of the polyimide obtained from the said diamine and tetracarboxylic dianhydride using the said terminal sealing agent after making tetracarboxylic dianhydride and diamine react, the method of adding the terminal sealing agent and continuing reaction, After the terminal sealing agent is added to the diamine and reacted, tetracarboxylic dianhydride may be added to continue the reaction, and tetracarboxylic dianhydride, diamine and the terminal sealing agent may be added and reacted to prepare the same. .
  • the polyimide precursor by which the terminal was sealed can be polymerized.
  • the polyimide precursor polymerization reaction may be carried out according to a conventional polyimide precursor polymerization method such as solution polymerization.
  • the reaction may be carried out in anhydrous conditions, the temperature during the polymerization may be carried out at -75 to 50 °C, preferably 0 to 40 °C.
  • the diamine may be carried out by adding an acid dianhydride in a state in which it is dissolved in an organic solvent, wherein diamine and acid dianhydride may be included in the content of about 10 to 30% by weight in the polymerization solvent, Accordingly the molecular weight can be adjusted.
  • organic solvent that can be used in the polymerization reaction specifically, gamma-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4 Ketones such as methyl-2-pentanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl a
  • sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide
  • Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide
  • Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide
  • Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone may be used alone or as a mixture, but is not limited thereto.
  • an aromatic hydrocarbon such as xylene or toluene may be further included and used.
  • the method for producing a polyimide film by using the prepared polyimide precursor, the polyimide precursor composition comprising the polyimide precursor and an organic solvent is applied to one side of the substrate and after the imidization and curing process, separated from the substrate Steps.
  • the polyimide precursor composition may be in the form of a solution in which a polyimide precursor is dissolved in an organic solvent, and in the case of having such a form, for example, when a polyimide precursor is synthesized in an organic solvent, the polyimide precursor composition
  • the polyimide precursor solution itself or the same solution obtained after silver polymerization may be further added, or the polyimide precursor solution obtained after the said superposition
  • polymerization may be diluted with another solvent.
  • the polyimide precursor composition may include solids in an amount such that the polyimide precursor composition has an appropriate viscosity in consideration of processability such as coating property in a film forming process, and the solid content is 5 to 20 wt% based on the total weight of the polyimide precursor composition. It may be included as. Alternatively, it may be desirable to adjust the polyimide precursor composition to have a viscosity of 400 to 50,000 cP. When the viscosity of the polyimide precursor composition may be less than 400 cP, and when the viscosity of the polyimide precursor composition is greater than 50,000 cP, fluidity may be lowered during manufacturing of the display substrate using the polyimide precursor composition, and thus the coating may not be uniformly applied. May cause problems in the manufacturing process.
  • a polyimide film may be prepared by applying the polyimide precursor composition prepared above to one surface of a substrate, heat imidizing and curing at a temperature of 80 ° C. to 500 ° C., and then separating from the substrate.
  • a glass, a metal substrate or a plastic substrate may be used as the substrate without particular limitation, and among these, the thermal and chemical stability is excellent during the imidization and curing process for the polyimide precursor, and without curing any release agent, It may be desirable to have a glass substrate that can be easily separated without damage to the polyimide-based film formed afterwards.
  • the coating step may be carried out according to a conventional coating method, specifically, spin coating method, bar coating method, roll coating method, air-knife method, gravure method, reverse roll method, kiss roll method, doctor blade method, Spray method, dipping method, brushing method and the like can be used.
  • spin coating method bar coating method, roll coating method, air-knife method, gravure method, reverse roll method, kiss roll method, doctor blade method, Spray method, dipping method, brushing method and the like can be used.
  • the continuous process is possible, and it may be more preferable to be carried out by a casting method that can increase the imidation ratio of the polyimide.
  • the polyimide precursor composition may be applied on the substrate in a thickness range such that the polyimide film to be produced has a thickness suitable for the display substrate.
  • a drying step for removing the solvent present in the polyimide precursor composition may be optionally further performed before the curing process.
  • the drying process may be carried out in accordance with a conventional method, specifically may be carried out at a temperature of 140 °C or less, or 80 °C to 140 °C.
  • a temperature of 140 °C or less or 80 °C to 140 °C.
  • the implementation temperature of a drying process is less than 80 degreeC, a drying process becomes long, and when it exceeds 140 degreeC, imidation advances rapidly and it is difficult to form polyimide film of uniform thickness.
  • the curing process may be performed by heat treatment at a temperature of 80 °C to 500 °C.
  • the curing process may be carried out by a multi-step heat treatment at various temperatures within the above temperature range.
  • the curing time during the curing process is not particularly limited, it may be carried out for 30 minutes to 60 minutes as an example.
  • a subsequent heat treatment step may be optionally further performed to increase the imidation ratio of the polyimide in the polyimide film to form a polyimide film having the above-described physical properties.
  • the subsequent heat treatment process is preferably carried out for 1 to 30 minutes at 200 °C or more, or 200 °C to 500 °C.
  • the subsequent heat treatment process may be performed once or may be performed in multiple stages two or more times. Specifically, it may be carried out in three steps including a first heat treatment at 200 to 220 ° C., a second heat treatment at 300 ° C. to 380 ° C., and a third heat treatment at 400 ° C. to 500 ° C., preferably final curing It may be prepared by curing for 30 minutes or more and 2 hours or less, preferably 30 minutes or more and 1 hour or less under the condition that the temperature is 450 ° C or more.
  • the polyimide film can be produced by peeling the polyimide film formed on the substrate from the substrate according to a conventional method.
  • the polyimide according to the present invention may have a glass transition temperature of about 360 ° C. or more. Since it has such excellent heat resistance, the film containing the said polyimide can maintain the outstanding heat resistance and mechanical property also with respect to the high temperature heat added during an element manufacturing process.
  • the polyimide film according to the present invention may have a thermal decomposition temperature (Td 1%) indicating a mass loss of 1% of 550 ° C. or more.
  • the polyimide film according to the present invention has excellent mechanical properties, for example, the elongation may be 20% or more, preferably 25% or more, and the tensile strength is 500 MPa or more, preferably 520. It may be at least MPa, more preferably at least 530 MPa, and the tensile modulus may be at least 10 GPa.
  • the present invention provides a polyimide film that is end-sealed with a terminal encapsulant containing phthalic anhydride, thereby exhibiting positive CTE values even at high temperatures, which may be caused by negative CTE (shrinkage) at high temperatures.
  • a polyimide film having a high transmittance characteristic preferably a polyimide film having a transmittance of 70% or more, and when manufacturing a device on the polyimide substrate described above, TFT through an align key Fabrication of the device can be made easier.
  • the polyimide according to the present invention is a substrate for a device, a cover substrate for a display, an optical film, an integrated circuit (IC) package, an adhesive film, a multilayer FPC (flexible printed circuit), a tape, a touch panel, It can be used in various fields such as a protective film for an optical disc.
  • IC integrated circuit
  • FPC flexible printed circuit
  • the present invention provides a flexible display device including the polyimide film.
  • the display device may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), and the like, and particularly a low temperature polycrystalline silicon that requires a high temperature process. It may be suitable for an OLED device using a) process, but is not limited thereto.
  • NMP N-methyl-2-pyrrolidone
  • p-PDA para phenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • PA phthalic anhydride
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • the polyimide precursor solution was spin coated onto a glass substrate.
  • the glass substrate coated with the polyimide precursor solution was placed in an oven and heated at a rate of 6 ° C./min, and a curing process was performed by maintaining 10 minutes at 120 ° C. and 55 minutes at 460 ° C. After completion of the curing process, the glass substrate was immersed in water, the film formed on the glass substrate was removed and dried at 100 ° C. in an oven to prepare a film of polyimide having a thickness of 10 ⁇ m.
  • NMP N-methyl-2-pyrrolidone
  • p-PDA para phenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • PA phthalic anhydride
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • p-PDA para phenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • PA phthalic anhydride
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • p-PDA para phenylenediamine
  • TFMB 2,2'-bis (trifluoromethyl) benzidine
  • PA phthalic anhydride
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the polyimide precursor solution was prepared by adding the organic solvent to the polyimide precursor prepared from the reaction so that the solid content concentration was 12.8 wt%.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the polyimide precursor solution was prepared by adding the organic solvent to the polyimide precursor prepared from the reaction so that the solid content concentration was 12.8 wt%.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the organic solvent was added to prepare a polyimide precursor solution such that the solid content concentration of the polyimide precursor solution prepared from the above reaction was 12.8% by weight.
  • a polyimide film having a thickness of 10 ⁇ m was prepared in the same manner as in Example 1.
  • the sample was fixed to the sample holder using a magnet and then mounted on the sample stage.
  • Perform z-> omega-> z align for alignment and fix the angle of incidence (w 0.4 °) for GIXRD (Grazing Incidence X-ray Diffraction) experiment, and perform detector scan within 5 ° ⁇ 2 ⁇ 70 °
  • the step size was 0.04 ° and the time / step was 2 seconds.
  • Equation 2 C, ⁇ and ⁇ represent the specific heat (J / g ⁇ K), density (g / cm 3 ) and thermal diffusivity (mm 2 / sec) of the polyimide film.
  • Thermal diffusivity was measured by using a LFA 467 Hyperflash at room temperature for the samples.
  • the standard sample holder was a 12.7 mm round holder, and graphite coated to increase light absorption at the front and heat dissipation at the back of the sample.
  • Density was measured using a microbalance (MSA125P, Satorius) and volume was determined using the respective length measurement method.
  • the film according to the present invention exhibited a crystallinity of 0.52, which is increased by more than 33% compared to the film of the comparative example.
  • the thermal conductivity increased by 2.8 times or more, as shown in the results of Table 1 and FIG. 3.
  • the film according to the present invention having a BPDA-pPDA-TFMB / PA skeleton and no siloxane repeating unit and having a crystallinity of 0.5 or more has excellent heat dissipation characteristics.

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Abstract

La présente invention concerne un substrat pour un dispositif d'affichage souple, le substrat possédant une valeur CTE positive sans détérioration de la résistance thermique même à une température de 350°C ou plus, par l'utilisation d'un polyimide obtenu à partir de la polymérisation d'éléments de polymérisation dans lesquels de la p-PDA en tant que diamine est ajoutée en excès par rapport à la s-BPDA en tant que dianhydride d'acide et un agent adhésif terminal contenant de l'anhydride phtalique (PA) est ajouté. De plus, un tel procédé de fabrication permet la production d'un film de polyimide, qui possède une transmittance supérieure à celle d'un film de polyimide fabriqué à l'aide d'une composition possédant simplement un excès d'une diamine, de sorte que les dispositifs TFT peuvent être fabriqués par l'intermédiaire de clés d'alignement plus facilement lorsque les dispositifs sont fabriqués sur des substrats de polyimide.
PCT/KR2019/000639 2018-05-14 2019-01-16 Film de polyimide pour substrat de dispositif d'affichage souple possédant d'excellentes caractéristiques de dissipation de chaleur WO2019221364A1 (fr)

Priority Applications (4)

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JP2020511988A JP7167412B2 (ja) 2018-05-14 2019-01-16 ポリイミドフィルムの製造方法
US16/649,311 US20200274084A1 (en) 2018-05-14 2019-01-16 Polyimide film for flexible display device substrate having excellent heat dissipation characteristics
CN201980004200.5A CN111094411A (zh) 2018-05-14 2019-01-16 具有优异的散热特性的用于柔性显示装置基底的聚酰亚胺膜
EP19803845.7A EP3656805A4 (fr) 2018-05-14 2019-01-16 Film de polyimide pour substrat de dispositif d'affichage souple possédant d'excellentes caractéristiques de dissipation de chaleur

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KR20180054983 2018-05-14
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KR1020180164186A KR102333188B1 (ko) 2018-05-14 2018-12-18 방열특성이 우수한 플렉서블 디스플레이 소자 기판용 폴리이미드 필름

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111403583A (zh) * 2020-03-20 2020-07-10 Tcl华星光电技术有限公司 一种散热膜的制备方法及显示装置
CN111635546A (zh) * 2020-06-24 2020-09-08 东莞东阳光科研发有限公司 一种含氟聚合物/聚酰亚胺复合薄膜的制备方法
CN112175185A (zh) * 2020-10-16 2021-01-05 吉林奥来德光电材料股份有限公司 一种聚酰胺酸溶液及其制备方法和含有其的聚酰亚胺薄膜的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090084772A (ko) * 2008-02-01 2009-08-05 우베 고산 가부시키가이샤 폴리이미드 필름 및 폴리이미드 필름의 제조방법
KR20140004655A (ko) * 2011-01-07 2014-01-13 도레이 카부시키가이샤 폴리아미드산 수지 조성물 및 그의 제조 방법
KR20150046463A (ko) * 2013-10-22 2015-04-30 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 및 표시소자
KR20170069190A (ko) * 2017-06-09 2017-06-20 코오롱인더스트리 주식회사 플라스틱 소재의 플렉서블 디스플레이 기판
KR20180054983A (ko) 2016-11-15 2018-05-25 삼성디스플레이 주식회사 유기 발광 표시 장치 및 그 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090084772A (ko) * 2008-02-01 2009-08-05 우베 고산 가부시키가이샤 폴리이미드 필름 및 폴리이미드 필름의 제조방법
KR20140004655A (ko) * 2011-01-07 2014-01-13 도레이 카부시키가이샤 폴리아미드산 수지 조성물 및 그의 제조 방법
KR20150046463A (ko) * 2013-10-22 2015-04-30 코오롱인더스트리 주식회사 폴리아믹산, 폴리이미드 및 표시소자
KR20180054983A (ko) 2016-11-15 2018-05-25 삼성디스플레이 주식회사 유기 발광 표시 장치 및 그 제조 방법
KR20170069190A (ko) * 2017-06-09 2017-06-20 코오롱인더스트리 주식회사 플라스틱 소재의 플렉서블 디스플레이 기판

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUANG SEN-BIAO PROPERTIES: "Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers", CHEM. RES. CHINESE UNIVERSITIES, vol. 28, no. 4, 2012, pages 752 - 756, XP055654291 *
See also references of EP3656805A4

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111403583A (zh) * 2020-03-20 2020-07-10 Tcl华星光电技术有限公司 一种散热膜的制备方法及显示装置
CN111635546A (zh) * 2020-06-24 2020-09-08 东莞东阳光科研发有限公司 一种含氟聚合物/聚酰亚胺复合薄膜的制备方法
CN111635546B (zh) * 2020-06-24 2022-04-29 东莞东阳光科研发有限公司 一种含氟聚合物/聚酰亚胺复合薄膜的制备方法
CN112175185A (zh) * 2020-10-16 2021-01-05 吉林奥来德光电材料股份有限公司 一种聚酰胺酸溶液及其制备方法和含有其的聚酰亚胺薄膜的制备方法

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